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The stereochemistry of the photo reaction products of tricarbonyl-η-6,6-dimethyl-fulvene-chromium(O) (1) with 7-methyl-and 7-methoxycycloheptatriene was studied by NMR-spectroscopy. Both trienes add to 1, displace a CO ligand, and form substituted dicarbonyl-η 3 -2-cycloheptadienylene-η 5 -2-cyclopentadienylidene-propane-chromium(0) complexes. With C 7 H 7 CH 3  only one isomer (3) is formed with the methyl-group in endo-position and the enyl system encompassing C(1′)-C(3′) of the seven membered ring. C 7 H 7 OCH 3  yields 3 isomers which were separated by column chromatography. 5 has the same constitution as 3. The isomers 4 and 5 bear the OCH 3 -group in e^o-position. The enyl system of 4 is located on C(1′)-C(3′), that of 6 on C(3′)-C(5′). 6 rearranges at room temperature to 4.

zeitschrift für naturforschung b

Photochemische Reaktionen von Übergangsmetall-Olefin-Komplexen, V [1]. Die Umsetzung von Tricarbonyl-η-6.6-dimethylfulven-chrom(0) mit 7-Methyl- und 7-Methoxycycloheptatrien / Photochemical Reactions of Transition Metal Olefin Complexes, V [1]. The Reactions of Tricarbonyl-η-6,6-dimethylfulvene-chromium(0) with 7-Methyl- and 7-Methoxycycloheptatriene